najoNanosystems: Physics, Chemistry, MathematicsНаносистемы: физика, химия, математика2220-80542305-7971Университет ИТМО10.17586/2220-8054-2024-15-6-837-854najo-181Research ArticleCHEMISTRY AND MATERIALS SCIENCEХИМИЯ И НАУКА О МАТЕРИАЛАХGranular Ni–Mo–W bulk hydrotreating catalyst: the effects from precursor calcinationГранулированные Ni-Mo-W массивные катализаторы гидроочистки: влияние прокаливания предшественникаhttps://orcid.org/0000-0003-2671-5146НадеинаК. А.NadeinaK. A.

пр. ак. Лаврентьева 5, 630090 Новосибирск

Ksenia A. Nadeina

Pr. Lavrentieva 5, 630090 Novosibirsk

lakmallow@catalysis.ruhttps://orcid.org/0000-0001-8898-9762ВатутинаЮ. В.VatutinaYu. V.

пр. ак. Лаврентьева 5, 630090 Новосибирск

Yuliya V. Vatutina

Pr. Lavrentieva 5, 630090 Novosibirsk

y.vatutina@catalysis.ruhttps://orcid.org/0000-0002-5005-0781МухачеваП. П.MukhachevaP. P.

пр. ак. Лаврентьева 5, 630090 Новосибирск

Polina P. Mukhacheva

Pr. Lavrentieva 5, 630090 Novosibirsk

mpp@catalysis.ruhttps://orcid.org/0000-0001-7450-3960БудукваС. В.BudukvaS. V.

пр. ак. Лаврентьева 5, 630090 Новосибирск

Sergey V. Budukva

Pr. Lavrentieva 5, 630090 Novosibirsk

zsm@catalysis.ruhttps://orcid.org/0000-0003-1476-9825ДаниловаИ. Г.DanilovaI. G.

пр. ак. Лаврентьева 5, 630090 Новосибирск

Irina G. Danilova

Pr. Lavrentieva 5, 630090 Novosibirsk

danig@catalysis.ruhttps://orcid.org/0000-0001-8808-0161ПахаруковаВ. П.PakharukovaV. P.

пр. ак. Лаврентьева 5, 630090 Новосибирск

Vera P. Pakharukova

Pr. Lavrentieva 5, 630090 Novosibirsk

verapakharukova@yandex.ruhttps://orcid.org/0000-0002-3230-3335ГерасимовЕ. Ю.GerasimovE. Yu.

пр. ак. Лаврентьева 5, 630090 Новосибирск

Evgeniy Yu. Gerasimov

Pr. Lavrentieva 5, 630090 Novosibirsk

gerasimov@catalysis.ruhttps://orcid.org/0000-0001-6897-7692ПанафидинМ. А.PanafidinM. A.

пр. ак. Лаврентьева 5, 630090 Новосибирск

Maxim A. Panafidin

Pr. Lavrentieva 5, 630090 Novosibirsk

mpanafidin@catalysis.ruhttps://orcid.org/0000-0002-8089-2357КлимовО. В.KlimovO. V.

пр. ак. Лаврентьева 5, 630090 Новосибирск

Oleg V. Klimov

Pr. Lavrentieva 5, 630090 Novosibirsk

klm@catalysis.ruИнститут катализа СО РАНBoreskov Institute of Catalysis SB RAS202405062025156837854Copyright © Nadeina K.A., Vatutina Y.V., Mukhacheva P.P., Budukva S.V., Danilova I.G., Pakharukova V.P., Gerasimov E.Y., Panafidin M.A., Klimov O.V., 20252025Надеина К.А., Ватутина Ю.В., Мухачева П.П., Будуква С.В., Данилова И.Г., Пахарукова В.П., Герасимов Е.Ю., Панафидин М.А., Климов О.В.Nadeina K.A., Vatutina Y.V., Mukhacheva P.P., Budukva S.V., Danilova I.G., Pakharukova V.P., Gerasimov E.Y., Panafidin M.A., Klimov O.V.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://nanojournal.ifmo.ru/jour/article/view/181

This paper presents a study on the effect of the Ni–Mo–W precursor calcination (300, 450 and 500 ◦C) on properties of granulated bulk Ni–Mo–W catalysts. The Ni–Mo–W precursor and bulk catalysts were studied by XRD, nitrogen adsorption-desorption method, CHNS analysis, thermal analysis, Raman spectroscopy, UV-Vis DR spectroscopy, HRTEM and XPS. It is shown that the increase in calcination temperature of the precursor to 500 ◦C leads to stepwise decomposition of citric acid, transformation of active metals and re-structurization of the samples. Active metals in sulfide catalysts are present in the bulk mixed or individual sulfides and interact with alumina binder to form “NiMoS-like” sulfide phase. Increased crystallinity of the precursor results in the enlargement of bulk nickel particles, capsulation of Mo and W and their rounding by Ni atoms. Catalysts testing in hydrotreatment of SRVGO demonstrates that the best choice of temperature regimes is 300 ◦C for the precursor.

В данной статье представлено исследование влияния прокаливания Ni-Mo-W предшественника (300, 450 и 500ºC) на свойства гранулированных массивных Ni-Mo-W катализаторов. Ni-Mo-W предшественник и массивные катализаторы были изучены методами РФА, адсорбции-десорбции азота, CHNS анализа, термического анализа, Рамановской спектроскопии, УФ-Вид ДО спектроскопии, ПЭМВР и РФЭС. Показано, что повышение температуры прокаливания предшественника до 500ºC приводит к ступенчатому разложению лимонной кислоты, трансформации активных металлов и реструктуризации образцов. Активные металлы в сульфидных катализаторах присутствуют в виде массивных смешанных или индивидуальных сульфидов и взаимодействуют со связующим оксидом алюминия с образованием «NiMoS-подобной» сульфидной фазы. Повышение кристалличности предшественника приводит к укрупнению массивных частиц никеля, капсулированию Mo и W и их окружению атомами Ni. Испытания катализаторов в гидроочистке прямогонного ВГО показывают, что оптимальным выбором температурных режимов для предшественника является 300ºC.

массивный катализаторNiMoWпрокаливаниеГДСГДНbulk catalystNiMoWcalcinationHDSHDNThe study was funded by the Russian Science Foundation according to the research project No. 22-73-10144 (https://rscf.ru/en/project/22-73-10144/).ReferencesTanimu A., Alhooshani K. Advanced Hydrodesulfurization Catalysts: A Review of Design and Synthesis. Energy and Fuels, 2019, 33, P. 2810– 2838.Tanimu A., Alhooshani K. Advanced Hydrodesulfurization Catalysts: A Review of Design and Synthesis. Energy and Fuels, 2019, 33, P. 2810– 2838.D´ıaz de Le´on J.N., Ramesh Kumar C., Ant´unez-Garc´ıa J., Fuentes-Moyado S. Recent Insights in Transition Metal Sulfide Hydrodesulfurization Catalysts for the Production of Ultra Low Sulfur Diesel: A Short Review. Catalysts, 2019, 9, 87.D´ıaz de Le´on J.N., Ramesh Kumar C., Ant´unez-Garc´ıa J., Fuentes-Moyado S. Recent Insights in Transition Metal Sulfide Hydrodesulfurization Catalysts for the Production of Ultra Low Sulfur Diesel: A Short Review. Catalysts, 2019, 9, 87.Topsøe H., Clausen B.S., Candia R., Wivel C., Mørup S. In situ M¨ossbauer emission spectroscopy studies of unsupported and supported sulfided Co-Mo hydrodesulfurization catalysts: Evidence for and nature of a Co–Mo–S phase. J. Catal., 1981, 68, P. 433–452.Topsøe H., Clausen B.S., Candia R., Wivel C., Mørup S. In situ M¨ossbauer emission spectroscopy studies of unsupported and supported sulfided Co-Mo hydrodesulfurization catalysts: Evidence for and nature of a Co–Mo–S phase. J. Catal., 1981, 68, P. 433–452.Lauritsen J.V., Kibsgaard J., Olesen G.H., Moses P.G., Hinnemann B., Helveg S., Nørskov J.K., Clausen B.S., Topsøe H., Lægsgaard E., Besenbacher F. Location and coordination of promoter atoms in Co- and Ni-promoted MoS2-based hydrotreating catalysts. J. Catal., 2007, 249, P. 220–233.Lauritsen J.V., Kibsgaard J., Olesen G.H., Moses P.G., Hinnemann B., Helveg S., Nørskov J.K., Clausen B.S., Topsøe H., Lægsgaard E., Besenbacher F. Location and coordination of promoter atoms in Co- and Ni-promoted MoS2-based hydrotreating catalysts. J. Catal., 2007, 249, P. 220–233.Plantenga F.L., Cerfontain R., Eijsbouts S., Houtert F., Anderson G.H., Miseo S., Soled S., Riley K., Fujita K., Inoue Y. “NEBULA”: A hydroprocessing catalyst with breakthrough activity. Stud. Surf. Sci. Catal., 2003, 145, P. 407–410.Plantenga F.L., Cerfontain R., Eijsbouts S., Houtert F., Anderson G.H., Miseo S., Soled S., Riley K., Fujita K., Inoue Y. “NEBULA”: A hydroprocessing catalyst with breakthrough activity. Stud. Surf. Sci. Catal., 2003, 145, P. 407–410.Eijsbouts S., Plantenga F., Leliveld B., Inoue Y., Fujita K. STARS and NEBULA – New Generations of Hydroprocessing Catalysts for the Production of Ultra Low Sulfur Diesel. Prepr. Symp. – Am. Chem. Soc., Div. Fuel Chem., 2003, 48, P. 494–495.Eijsbouts S., Plantenga F., Leliveld B., Inoue Y., Fujita K. STARS and NEBULA – New Generations of Hydroprocessing Catalysts for the Production of Ultra Low Sulfur Diesel. Prepr. Symp. – Am. Chem. Soc., Div. Fuel Chem., 2003, 48, P. 494–495.Thomazeau C., Geantet C., Lacroix M., Danot M., Harl´e V., Raybaud P. Predictive approach for the design of improved HDT catalysts: γ-Alumina supported (Ni, Co) promoted Mo1−xWxS2 active phases. Appl. Catal. A Gen., 2007, 322, P. 92–97.Thomazeau C., Geantet C., Lacroix M., Danot M., Harl´e V., Raybaud P. Predictive approach for the design of improved HDT catalysts: γ-Alumina supported (Ni, Co) promoted Mo1−xWxS2 active phases. Appl. Catal. A Gen., 2007, 322, P. 92–97.Cervantes-Gaxiola M.E., Arroyo-Albiter M., P´erez-Larios A., Balbuena P.B., Espino-Valencia J. Experimental and theoretical study of NiMoW, NiMo, and NiW sulfide catalysts supported on an AlTiMg mixed oxide during the hydrodesulfurization of dibenzothiophene. Fuel, 2013, 113, P. 733–743.Cervantes-Gaxiola M.E., Arroyo-Albiter M., P´erez-Larios A., Balbuena P.B., Espino-Valencia J. Experimental and theoretical study of NiMoW, NiMo, and NiW sulfide catalysts supported on an AlTiMg mixed oxide during the hydrodesulfurization of dibenzothiophene. Fuel, 2013, 113, P. 733–743.Krebs E., Silvi B., Daudin A., Raybaud P. A DFT study of the origin of the HDS/HydO selectivity on Co(Ni)MoS active phases. J. Catal., 2008, 260, P. 276–287.Krebs E., Silvi B., Daudin A., Raybaud P. A DFT study of the origin of the HDS/HydO selectivity on Co(Ni)MoS active phases. J. Catal., 2008, 260, P. 276–287.Shan S., Liu H., Yue Y., Shi G., Bao X. Trimetallic WMoNi diesel ultra-deep hydrodesulfurization catalysts with enhanced synergism prepared from inorganic–organic hybrid nanocrystals. J. Catal., 2016, 344, P. 325–333.Shan S., Liu H., Yue Y., Shi G., Bao X. Trimetallic WMoNi diesel ultra-deep hydrodesulfurization catalysts with enhanced synergism prepared from inorganic–organic hybrid nanocrystals. J. Catal., 2016, 344, P. 325–333.Varakin A.N., Mozhaev A.V., Pimerzin A.A., Nikulshin P.A. Comparable investigation of unsupported MoS2 hydrodesulfurization catalysts prepared by different techniques: Advantages of support leaching method. Appl. Catal. B Environ., 2018, 238, P. 498–508.Varakin A.N., Mozhaev A.V., Pimerzin A.A., Nikulshin P.A. Comparable investigation of unsupported MoS2 hydrodesulfurization catalysts prepared by different techniques: Advantages of support leaching method. Appl. Catal. B Environ., 2018, 238, P. 498–508.Yin C., Dong C., Kong Y., Li K., Zhang H., Liu D., Liu C. Effects of Aging Treatment on the Hydrotreating Performance of the Unsupported Catalyst. Ind. & Eng. Chem. Res., 2019, 58, P. 2683–2688.Yin C., Dong C., Kong Y., Li K., Zhang H., Liu D., Liu C. Effects of Aging Treatment on the Hydrotreating Performance of the Unsupported Catalyst. Ind. & Eng. Chem. Res., 2019, 58, P. 2683–2688.Nadeina K.A., Budukva S.V., Vatutina Y.V., Mukhacheva P.P., Gerasimov E.Y., Pakharukova V.P., Prosvirin I.P., Larina T.V., Klimov O.V., Noskov A.S., Atuchin V.V. Optimal Choice of the Preparation Procedure and Precursor Composition for a Bulk Ni–Mo–W Catalyst. Inorganics, 2023, 11, 89.Nadeina K.A., Budukva S.V., Vatutina Y.V., Mukhacheva P.P., Gerasimov E.Y., Pakharukova V.P., Prosvirin I.P., Larina T.V., Klimov O.V., Noskov A.S., Atuchin V.V. Optimal Choice of the Preparation Procedure and Precursor Composition for a Bulk Ni–Mo–W Catalyst. Inorganics, 2023, 11, 89.Mukhacheva P.P., Vatutina Y.V., Nadeina K.A., Budukva S.V., Pakharukova V.P., Danilova I.G., Panafidin M.A., Klimov O.V., Noskov A.S. Effects of Heat Treatment Temperature on the Physicochemical Properties and Catalytic Performance of Bulk Ni–Mo–W Catalysts. Pet. Chem., 2023, 63, P. 1302–1310.Mukhacheva P.P., Vatutina Y.V., Nadeina K.A., Budukva S.V., Pakharukova V.P., Danilova I.G., Panafidin M.A., Klimov O.V., Noskov A.S. Effects of Heat Treatment Temperature on the Physicochemical Properties and Catalytic Performance of Bulk Ni–Mo–W Catalysts. Pet. Chem., 2023, 63, P. 1302–1310.Wang L., Zhang Y., Zhang Y., Jiang Z., Li C. Ultra-Deep Hydrodesulfurization of Diesel Fuels on Trimetallic NiMoW Sulfide Catalysts. Chem. – A Eur. J., 2009, 15, P. 12571–12575.Wang L., Zhang Y., Zhang Y., Jiang Z., Li C. Ultra-Deep Hydrodesulfurization of Diesel Fuels on Trimetallic NiMoW Sulfide Catalysts. Chem. – A Eur. J., 2009, 15, P. 12571–12575.Chowdari R.K., D´ıaz de Le´on J.N., Fuentes-Moyado S. Effect of sulfidation conditions on the unsupported flower-like bimetallic oxide microspheres for the hydrodesulfurization of dibenzothiophene. Catal. Today, 2022, 394–396, P. 13–24.Chowdari R.K., D´ıaz de Le´on J.N., Fuentes-Moyado S. Effect of sulfidation conditions on the unsupported flower-like bimetallic oxide microspheres for the hydrodesulfurization of dibenzothiophene. Catal. Today, 2022, 394–396, P. 13–24.Ouyang X., Kuperman A. Multi-metallic bulk hydroprocessing catalysts, Patent 2022269376, 2021.Ouyang X., Kuperman A. Multi-metallic bulk hydroprocessing catalysts, Patent 2022269376, 2021.Liu H., Yin C., Liu B., Li X., Li Y., Chai Y., Liu C. Effect of Calcination Temperature of Unsupported NiMo Catalysts on the Hydrodesulfurization of Dibenzothiophene. Energy & Fuels, 2014, 28, P. 2429–2436.Liu H., Yin C., Liu B., Li X., Li Y., Chai Y., Liu C. Effect of Calcination Temperature of Unsupported NiMo Catalysts on the Hydrodesulfurization of Dibenzothiophene. Energy & Fuels, 2014, 28, P. 2429–2436.Yang C., Hu A., Dai Q., Yang Q., Hou R., Liu Z. Study on the Performance of Ni–MoS2 Catalysts with Different MoS2 Structures for Dibenzothiophene Hydrodesulfurization. ACS Omega, 2023, 8, P. 41182–41193.Yang C., Hu A., Dai Q., Yang Q., Hou R., Liu Z. Study on the Performance of Ni–MoS2 Catalysts with Different MoS2 Structures for Dibenzothiophene Hydrodesulfurization. ACS Omega, 2023, 8, P. 41182–41193.Nadeina K.A., Budukva S.V., Vatutina Y.V., Mukhacheva P.P., Gerasimov E.Y., Pakharukova V.P., Klimov O.V., NoskovA.S. Unsupported Ni– Mo–W Hydrotreating Catalyst: Influence of the Atomic Ratio of Active Metals on the HDS and HDN Activity. Catalysts, 2022, 12, 1671.Nadeina K.A., Budukva S.V., Vatutina Y.V., Mukhacheva P.P., Gerasimov E.Y., Pakharukova V.P., Klimov O.V., NoskovA.S. Unsupported Ni– Mo–W Hydrotreating Catalyst: Influence of the Atomic Ratio of Active Metals on the HDS and HDN Activity. Catalysts, 2022, 12, 1671.Danilevich V.V., Nadeina K.A., Gerasimov E.Y., Shefer K.I., Klimov O.V., Noskov A.S. Synthesis and characterization of lanthanum-modified pseudoboehmite – The precursor of alumina supports and catalysts. Microporous Mesoporous Mater., 2022, 335, 111800.Danilevich V.V., Nadeina K.A., Gerasimov E.Y., Shefer K.I., Klimov O.V., Noskov A.S. Synthesis and characterization of lanthanum-modified pseudoboehmite – The precursor of alumina supports and catalysts. Microporous Mesoporous Mater., 2022, 335, 111800.Thommes M., Kaneko K., Neimark A.V., Olivier J.P., Rodriguez-Reinoso F., Rouquerol J., Sing K.S.W. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl. Chem., 2015, 87, P. 1051–1069.Thommes M., Kaneko K., Neimark A.V., Olivier J.P., Rodriguez-Reinoso F., Rouquerol J., Sing K.S.W. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl. Chem., 2015, 87, P. 1051–1069.Moulder J.F. Handbook of X-ray Photoelectron Spectroscopy, Physical Electronics Division, Perkin-Elmer Corporation, 1992.Moulder J.F. Handbook of X-ray Photoelectron Spectroscopy, Physical Electronics Division, Perkin-Elmer Corporation, 1992.Scofield J.H. Hartree-Slater subshell photoionization cross-sections at 1254 and 1487 eV. J. Electron Spectros. Relat. Phenomena, 1976, 8, P. 129– 137.Scofield J.H. Hartree-Slater subshell photoionization cross-sections at 1254 and 1487 eV. J. Electron Spectros. Relat. Phenomena, 1976, 8, P. 129– 137.Gajbhiye N.S., Balaji G. Synthesis, reactivity, and cations inversion studies of nanocrystalline MnFe2O4 particles. Thermochim. Acta, 2002, 385, P. 143–151.Gajbhiye N.S., Balaji G. Synthesis, reactivity, and cations inversion studies of nanocrystalline MnFe2O4 particles. Thermochim. Acta, 2002, 385, P. 143–151.Bocher L., Aguirre M.H., Robert R., Trottmann M., Logvinovich D., Hug P., Weidenkaff A. Chimie douce synthesis and thermochemical characterization of mesoporous perovskite-type titanate phases. Thermochim. Acta, 2007, 457, P. 11–19.Bocher L., Aguirre M.H., Robert R., Trottmann M., Logvinovich D., Hug P., Weidenkaff A. Chimie douce synthesis and thermochemical characterization of mesoporous perovskite-type titanate phases. Thermochim. Acta, 2007, 457, P. 11–19.Rajendran M., Rao M.S. Formation of BaTiO3 from Citrate Precursor. J. Solid State Chem.,1994, 113, P. 239–247.Rajendran M., Rao M.S. Formation of BaTiO3 from Citrate Precursor. J. Solid State Chem.,1994, 113, P. 239–247.Rajendran M., Rao S.M. Synthesis and characterization of barium bis(citrato) oxozirconate(IV) tetrahydrate: A new molecular precursor for fine particle BaZrO3. J. Mater. Res., 1994, 9, P. 2277–2284.Rajendran M., Rao S.M. Synthesis and characterization of barium bis(citrato) oxozirconate(IV) tetrahydrate: A new molecular precursor for fine particle BaZrO3. J. Mater. Res., 1994, 9, P. 2277–2284.Kov´acs T.N., Hunyadi D., de Lucena A.L.A., Szil´agyi I.M. Thermal decomposition of ammonium molybdates. J. Therm. Anal. Calorim., 2016, 124, P. 1013–1021.Kov´acs T.N., Hunyadi D., de Lucena A.L.A., Szil´agyi I.M. Thermal decomposition of ammonium molybdates. J. Therm. Anal. Calorim., 2016, 124, P. 1013–1021.Fait M.J.G., Lunk H.-J., Feist M., Schneider M., Dann J.N., Frisk T. Thermal decomposition of ammonium paratungstate tetrahydrate under non-reducing conditions: Characterization by thermal analysis, X-ray diffraction and spectroscopic methods. Thermochim. Acta, 2008, 469, P. 12–22.Fait M.J.G., Lunk H.-J., Feist M., Schneider M., Dann J.N., Frisk T. Thermal decomposition of ammonium paratungstate tetrahydrate under non-reducing conditions: Characterization by thermal analysis, X-ray diffraction and spectroscopic methods. Thermochim. Acta, 2008, 469, P. 12–22.Hunyadi D., Saj´o I., Szil´agyi I.M. Structure and thermal decomposition of ammonium metatungstate. J. Therm. Anal. Calorim., 2014, 116, P. 329– 337.Hunyadi D., Saj´o I., Szil´agyi I.M. Structure and thermal decomposition of ammonium metatungstate. J. Therm. Anal. Calorim., 2014, 116, P. 329– 337.Marafi M., Stanislaus A. Influence of catalyst acidity and feedstock quality on hydrotreating catalyst deactivation by coke deposition. Pet. Sci. Technol., 2001, 19, P. 697–710.Marafi M., Stanislaus A. Influence of catalyst acidity and feedstock quality on hydrotreating catalyst deactivation by coke deposition. Pet. Sci. Technol., 2001, 19, P. 697–710.Dychalska A., Popielarski P., Frank´ow W., Fabisiak K., Paprocki K., Szybowicz M. Study of CVD diamond layers with amorphous carbon admixture by Raman scattering spectroscopy. Mater. Sci., 2015, 33.Dychalska A., Popielarski P., Frank´ow W., Fabisiak K., Paprocki K., Szybowicz M. Study of CVD diamond layers with amorphous carbon admixture by Raman scattering spectroscopy. Mater. Sci., 2015, 33.Guichard B., Roy-Auberger M., Devers E., Rebours B., Quoineaud A.A., Digne M. Characterization of aged hydrotreating catalysts. Part I: Coke depositions, study on the chemical nature and environment. Appl. Catal. A Gen., 2009, 367, P. 1–8.Guichard B., Roy-Auberger M., Devers E., Rebours B., Quoineaud A.A., Digne M. Characterization of aged hydrotreating catalysts. Part I: Coke depositions, study on the chemical nature and environment. Appl. Catal. A Gen., 2009, 367, P. 1–8.Gonz´alez-Cort´es S.L., Qian Y., Almegren H.A., Xiao T., Kuznetsov V.L., Edwards P.P. Citric acid-assisted synthesis of γ-alumina-supported high loading CoMo sulfide catalysts for the hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) reactions. Appl. Petrochemical Res., 2015, 5, P. 181–197.Gonz´alez-Cort´es S.L., Qian Y., Almegren H.A., Xiao T., Kuznetsov V.L., Edwards P.P. Citric acid-assisted synthesis of γ-alumina-supported high loading CoMo sulfide catalysts for the hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) reactions. Appl. Petrochemical Res., 2015, 5, P. 181–197.Tian H., Roberts C.A., Wachs I.E. Molecular Structural Determination of Molybdena in Different Environments: Aqueous Solutions, Bulk Mixed Oxides, and Supported MoO3 Catalysts. J. Phys. Chem. C, 2010, 114, P. 14110–14120.Tian H., Roberts C.A., Wachs I.E. Molecular Structural Determination of Molybdena in Different Environments: Aqueous Solutions, Bulk Mixed Oxides, and Supported MoO3 Catalysts. J. Phys. Chem. C, 2010, 114, P. 14110–14120.Goetze J., Meirer F., Yarulina I., Gascon J., Kapteijn F., Ruiz-Mart´ınez J., Weckhuysen B.M. Insights into the Activity and Deactivation of the Methanol-to-Olefins Process over Different Small-Pore Zeolites As Studied with Operando UV-vis Spectroscopy. ACS Catal., 2017, 7, P. 4033– 4046.Goetze J., Meirer F., Yarulina I., Gascon J., Kapteijn F., Ruiz-Mart´ınez J., Weckhuysen B.M. Insights into the Activity and Deactivation of the Methanol-to-Olefins Process over Different Small-Pore Zeolites As Studied with Operando UV-vis Spectroscopy. ACS Catal., 2017, 7, P. 4033– 4046.Ross-Medgaarden E.I., Wachs I.E. Structural Determination of Bulk and Surface Tungsten Oxides with UV-vis Diffuse Reflectance Spectroscopy and Raman Spectroscopy. J. Phys. Chem. C, 2007, 111, P. 15089–15099.Ross-Medgaarden E.I., Wachs I.E. Structural Determination of Bulk and Surface Tungsten Oxides with UV-vis Diffuse Reflectance Spectroscopy and Raman Spectroscopy. J. Phys. Chem. C, 2007, 111, P. 15089–15099.Garbarino G., Riani P., Infantes-Molina A., Rodr´ıguez-Castell´on E., Busca G. On the detectability limits of nickel species on NiO/γ-Al2O3 catalytic materials. Appl. Catal. A Gen., 2016, 525, P. 180–189.Garbarino G., Riani P., Infantes-Molina A., Rodr´ıguez-Castell´on E., Busca G. On the detectability limits of nickel species on NiO/γ-Al2O3 catalytic materials. Appl. Catal. A Gen., 2016, 525, P. 180–189.Jeziorowski H., Knoezinger H. Raman and ultraviolet spectroscopic characterization of molybdena on alumina catalysts. J. Phys. Chem., 1979, 83, P. 1166–1173.Jeziorowski H., Knoezinger H. Raman and ultraviolet spectroscopic characterization of molybdena on alumina catalysts. J. Phys. Chem., 1979, 83, P. 1166–1173.da Silva V.L.S., Frety R., Schmal M. Activation and Regeneration of a NiMo/Al2O3 Hydrotreatment Catalyst. Ind. Eng. Chem. Res., 1994, 33, P. 1692–1699.da Silva V.L.S., Frety R., Schmal M. Activation and Regeneration of a NiMo/Al2O3 Hydrotreatment Catalyst. Ind. Eng. Chem. Res., 1994, 33, P. 1692–1699.Romanova T.S., Nadeina K.A., Danilova I.G., Danilevich V.V., Pakharukova V.P., Gabrienko A.A., Glazneva T.S., Gerasimov E.Y., Prosvirin I.P., Vatutina Y.V., Kazakov M.O., Klimov O.V., Noskov A.S. Modification of HDT catalysts of FCC feedstock by adding silica to the kneading paste of alumina support: Advantages and disadvantages. Fuel, 2022, 324, 124555.Romanova T.S., Nadeina K.A., Danilova I.G., Danilevich V.V., Pakharukova V.P., Gabrienko A.A., Glazneva T.S., Gerasimov E.Y., Prosvirin I.P., Vatutina Y.V., Kazakov M.O., Klimov O.V., Noskov A.S. Modification of HDT catalysts of FCC feedstock by adding silica to the kneading paste of alumina support: Advantages and disadvantages. Fuel, 2022, 324, 124555.Mohamed M.M., Ahmed S.A., Khairou K.S. Unprecedented high photocatalytic activity of nanocrystalline WO3/NiWO4 hetero-junction towards dye degradation: Effect of template and synthesis conditions. Appl. Catal. B Environ., 2014, 150–151, P. 63–73.Mohamed M.M., Ahmed S.A., Khairou K.S. Unprecedented high photocatalytic activity of nanocrystalline WO3/NiWO4 hetero-junction towards dye degradation: Effect of template and synthesis conditions. Appl. Catal. B Environ., 2014, 150–151, P. 63–73.Leonova K.A., Klimov O.V., Kochubey D.I., Chesalov Y.A., Gerasimov E.Y., Prosvirin I.P., Noskov A.S. Optimal pretreatment conditions for Co–Mo hydrotreatment catalysts prepared using ethylenediamine as a chelating agent. Catal. Today, 2014, 220–222, P. 327–336.Leonova K.A., Klimov O.V., Kochubey D.I., Chesalov Y.A., Gerasimov E.Y., Prosvirin I.P., Noskov A.S. Optimal pretreatment conditions for Co–Mo hydrotreatment catalysts prepared using ethylenediamine as a chelating agent. Catal. Today, 2014, 220–222, P. 327–336.Bukhtiyarova G.A., Klimov O.V., Kochubey D.I., Noskov A.S., Pashigreva A.V. EXAFS study of oxide precursors of the high active Co–Mo hydrotreating catalysts: Effect of drying conditions. Nucl. Instruments Methods Phys. Res. Sect. A Accel. Spectrometers, Detect. Assoc. Equip., 2009, 603, P. 119–121.Bukhtiyarova G.A., Klimov O.V., Kochubey D.I., Noskov A.S., Pashigreva A.V. EXAFS study of oxide precursors of the high active Co–Mo hydrotreating catalysts: Effect of drying conditions. Nucl. Instruments Methods Phys. Res. Sect. A Accel. Spectrometers, Detect. Assoc. Equip., 2009, 603, P. 119–121.Courty P., Ajot H., Marcilly C., Delmon B. Oxydes mixtes ou en solution solide sous forme tr`es divis´ee obtenus par d´ecomposition thermique de pr´ecurseurs amorphes. Powder Technol., 1973, 7, P. 21–38.Courty P., Ajot H., Marcilly C., Delmon B. Oxydes mixtes ou en solution solide sous forme tr`es divis´ee obtenus par d´ecomposition thermique de pr´ecurseurs amorphes. Powder Technol., 1973, 7, P. 21–38.Leonova K.A., Klimov O.V., Kochubey D.I., Chesalov Y.A., Gerasimov E.Y., Prosvirin I.P., Noskov A.S. Optimal pretreatment conditions for Co–Mo hydrotreatment catalysts prepared using ethylenediamine as a chelating agent. Catal. Today, 2014, 220–222, P. 327–336.Leonova K.A., Klimov O.V., Kochubey D.I., Chesalov Y.A., Gerasimov E.Y., Prosvirin I.P., Noskov A.S. Optimal pretreatment conditions for Co–Mo hydrotreatment catalysts prepared using ethylenediamine as a chelating agent. Catal. Today, 2014, 220–222, P. 327–336.Guzm´an-Castillo M.L., Bokhimi X., Toledo-Antonio A., Salmones-Bl´asquez J., Hern´andez-Beltr´an F. Effect of Boehmite Crystallite Size and Steaming on Alumina Properties. J. Phys. Chem. B, 2001, 105, P. 2099–2106.Guzm´an-Castillo M.L., Bokhimi X., Toledo-Antonio A., Salmones-Bl´asquez J., Hern´andez-Beltr´an F. Effect of Boehmite Crystallite Size and Steaming on Alumina Properties. J. Phys. Chem. B, 2001, 105, P. 2099–2106.Boumaza A., Favaro L., L´edion J., Sattonnay G., Brubach J.B., Berthet P., Huntz A.M., Roy P., T´etot R. Transition alumina phases induced by heat treatment of boehmite: An X-ray diffraction and infrared spectroscopy study. J. Solid State Chem., 2009, 182, P. 1171–1176.Boumaza A., Favaro L., L´edion J., Sattonnay G., Brubach J.B., Berthet P., Huntz A.M., Roy P., T´etot R. Transition alumina phases induced by heat treatment of boehmite: An X-ray diffraction and infrared spectroscopy study. J. Solid State Chem., 2009, 182, P. 1171–1176.Liu Q., Wang A., Wang X., Zhang T. Mesoporous γ-alumina synthesized by hydro-carboxylic acid as structure-directing agent. Microporous Mesoporous Mater., 2006, 92, P. 10–21.Liu Q., Wang A., Wang X., Zhang T. Mesoporous γ-alumina synthesized by hydro-carboxylic acid as structure-directing agent. Microporous Mesoporous Mater., 2006, 92, P. 10–21.Tichit D., El Alami D., Figueras F. Influence of the Preparation and of the Activation Treatments on the Catalytic Activity of Mechanical Mixtures of Sulfated Zirconia and Pt/Al2O3. J. Catal.,1996, 163, P. 18–27.Tichit D., El Alami D., Figueras F. Influence of the Preparation and of the Activation Treatments on the Catalytic Activity of Mechanical Mixtures of Sulfated Zirconia and Pt/Al2O3. J. Catal.,1996, 163, P. 18–27.Ozkan U., Schrader G.L. NiMoO4 selective oxidation catalysts containing excess MoO3 for the conversion of C4 hydrocarbons to maleic anhydride: I. Preparation and characterization. J. Catal.,1985, 95, P. 120–136.Ozkan U., Schrader G.L. NiMoO4 selective oxidation catalysts containing excess MoO3 for the conversion of C4 hydrocarbons to maleic anhydride: I. Preparation and characterization. J. Catal.,1985, 95, P. 120–136.Pampararo G., Garbarino G., Ardoino N., Riani P., Busca G. A study of molybdena catalysts in ethanol oxidation. Part 1. Unsupported and silica-supported MoO3. J. Chem. Technol. Biotechnol., 2021, 96.Pampararo G., Garbarino G., Ardoino N., Riani P., Busca G. A study of molybdena catalysts in ethanol oxidation. Part 1. Unsupported and silica-supported MoO3. J. Chem. Technol. Biotechnol., 2021, 96.Horsley J.A., Wachs I.E., Brown J.M., Via G.H., Hardcastle F.D. Structure of surface tungsten oxide species in the tungsten trioxide/alumina supported oxide system from x-ray absorption near-edge spectroscopy and Raman spectroscopy. J. Phys. Chem., 1987, 91, P. 4014–4020.Horsley J.A., Wachs I.E., Brown J.M., Via G.H., Hardcastle F.D. Structure of surface tungsten oxide species in the tungsten trioxide/alumina supported oxide system from x-ray absorption near-edge spectroscopy and Raman spectroscopy. J. Phys. Chem., 1987, 91, P. 4014–4020.Busca G. Differentiation of mono-oxo and polyoxo and of monomeric and polymeric vanadate, molybdate and tungstate species in metal oxide catalysts by IR and Raman spectroscopy. J. Raman Spectrosc., 2002, 33, P. 348–358.Busca G. Differentiation of mono-oxo and polyoxo and of monomeric and polymeric vanadate, molybdate and tungstate species in metal oxide catalysts by IR and Raman spectroscopy. J. Raman Spectrosc., 2002, 33, P. 348–358.Mukhacheva P.P., Vatutina Y.V., Nadeina K.A., Budukva S.V., Panafidin M.A., Pakharukova V.P., Parfenov M.V., Gerasimov E.Y., Klimov O.V., Noskov A.S. Comparison of the HDS DBT Reaction Using Bulk and Supported Catalysts. Chim. Techno Acta, 2024, 11, 202411206.Mukhacheva P.P., Vatutina Y.V., Nadeina K.A., Budukva S.V., Panafidin M.A., Pakharukova V.P., Parfenov M.V., Gerasimov E.Y., Klimov O.V., Noskov A.S. Comparison of the HDS DBT Reaction Using Bulk and Supported Catalysts. Chim. Techno Acta, 2024, 11, 202411206.Saih Y., Segawa K. Catalytic activity of CoMo catalysts supported on boron-modified alumina for the hydrodesulphurization of dibenzothiophene and 4.6-dimethyldibenzothiophene. Appl. Catal. A Gen., 2009, 353, P. 258–265.Saih Y., Segawa K. Catalytic activity of CoMo catalysts supported on boron-modified alumina for the hydrodesulphurization of dibenzothiophene and 4.6-dimethyldibenzothiophene. Appl. Catal. A Gen., 2009, 353, P. 258–265.Okamoto Y., Nakano H., Shimokawa T., Imanaka T., Teranishi S. Stabilization effect of Co for Mo phase in Co-MoAl2O3 hydrodesulfurization catalysts studied with X-Ray photoelectron spectroscopy. J. Catal., 1977, 50, P. 447–454.Okamoto Y., Nakano H., Shimokawa T., Imanaka T., Teranishi S. Stabilization effect of Co for Mo phase in Co-MoAl2O3 hydrodesulfurization catalysts studied with X-Ray photoelectron spectroscopy. J. Catal., 1977, 50, P. 447–454.Ben Tayeb K., Lamonier C., Lancelot C., Fournier M., Payen E., Bonduelle A., Bertoncini F. Study of the active phase of NiW hydrocracking sulfided catalysts obtained from an innovative heteropolyanion based preparation. Catal. Today, 2010, 150, P. 207–212.Ben Tayeb K., Lamonier C., Lancelot C., Fournier M., Payen E., Bonduelle A., Bertoncini F. Study of the active phase of NiW hydrocracking sulfided catalysts obtained from an innovative heteropolyanion based preparation. Catal. Today, 2010, 150, P. 207–212.Orsini G., Tricoli V. Facile nonhydrolytic sol–gel route to mesoporous mixed-conducting tungsten oxide. J. Mater. Chem., 2011, 21, P. 14530– 14542.Orsini G., Tricoli V. Facile nonhydrolytic sol–gel route to mesoporous mixed-conducting tungsten oxide. J. Mater. Chem., 2011, 21, P. 14530– 14542.Lorenz M., Schulze M. XPS analysis of electrochemically oxidized nickel surfaces. J. Anal. Chem., 1999, 365, P. 154–157.Lorenz M., Schulze M. XPS analysis of electrochemically oxidized nickel surfaces. J. Anal. Chem., 1999, 365, P. 154–157.Kazakova M.A., Kuznetsov V.L., Bokova-Sirosh S.N., Krasnikov D.V., Golubtsov G.V., Romanenko A.I., Prosvirin I.P., Ishchenko A.V., Orekhov A.S., Chuvilin A.L., Obraztsova E.D. Fe–Mo and Co–Mo Catalysts with Varying Composition for Multi-Walled Carbon Nanotube Growth. Phys. Status Solidi, 2018, 255, 1700260.Kazakova M.A., Kuznetsov V.L., Bokova-Sirosh S.N., Krasnikov D.V., Golubtsov G.V., Romanenko A.I., Prosvirin I.P., Ishchenko A.V., Orekhov A.S., Chuvilin A.L., Obraztsova E.D. Fe–Mo and Co–Mo Catalysts with Varying Composition for Multi-Walled Carbon Nanotube Growth. Phys. Status Solidi, 2018, 255, 1700260.Klimov O.V., Nadeina K.A., Vatutina Y.V., Stolyarova E.A., Danilova I.G., Gerasimov E.Y., Prosvirin I.P., NoskovA.S. CoMo/Al2O3 hydrotreating catalysts of diesel fuel with improved hydrodenitrogenation activity. Catal. Today, 2018, 307, P. 73–83.Klimov O.V., Nadeina K.A., Vatutina Y.V., Stolyarova E.A., Danilova I.G., Gerasimov E.Y., Prosvirin I.P., NoskovA.S. CoMo/Al2O3 hydrotreating catalysts of diesel fuel with improved hydrodenitrogenation activity. Catal. Today, 2018, 307, P. 73–83.Bremmer G.M., van Haandel L., Hensen E.J.M., Frenken J.W.M., Kooyman P.J. The effect of oxidation and resulfidation on (Ni/Co)MoS2 hydrodesulfurisation catalysts. Appl. Catal. B Environ., 2019, 243, P. 145–150.Bremmer G.M., van Haandel L., Hensen E.J.M., Frenken J.W.M., Kooyman P.J. The effect of oxidation and resulfidation on (Ni/Co)MoS2 hydrodesulfurisation catalysts. Appl. Catal. B Environ., 2019, 243, P. 145–150.

The authors declare that there are no conflicts of interest present.